Soluble self-orienting materials and conductive polymer compositions having the same

ABSTRACT

The present invention relates to an electrically conductive polymer, and more particularly to an additive for enhancing electrical conductivity of the polymer and electrically conductive polymer composition containing the additive. The present invention provides a soluble self-orienting material (SOM) and an electrically conductive polymer composition containing the SOM. The SOM can be provided as a form of a monomer having an aromatic ring with various polarity, flexible side chain and hydrophilic dibasic acid, as a form of a complex consisting of the monomers linked by a hydrogen bond or a metal coordinate bond or as a form of a whole aromatic polymer having —NRCO—, —NROSO—(R: side chain including —H, —CO 2 H, —(CH 2 )nSO 3 H, —(CH 2 )nCO 2 H or -tert-butyloxycarbonyl) and —OCO—. And also, the composition of the present invention have higher electrical conductivity, in excess of 103 S/cm, than a conventional conductive polymer, and also have improved processability.

CROSS REFERENCE TO RELATED APPLICATION

This application is the U.S. National Stage of International ApplicationPCT/KR02/00311, filed Feb. 26, 2002, which in turn claims priority fromKorean Patent Application 2001/14519, filed Mar. 21, 2001.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to conductive polymers, and moreparticularly it relates to an additive for enhancing electricalconductivity of the conductive polymer which forms a conductive polymercomposition with said additive.

DISCUSSION OF RELATED ART

Most conductive polymers show a strong tendency to polarize and havecommonly conjugated double bond that makes an inter-molecular forceremarkably strong by dispersion force among electrons. By moving chargesthrough doping step which adds an electron donor or an electronacceptor, the polymers get to conductive polymer salt with conductivevalues of over 10⁻⁸ S/cm.

The conductive polymers are applicable as an EMI shielding material, anantistatic material, an anticorrosive material, a static dischargematerial, and the like.

The advantage of the conductive polymers is that they can be variouslyprocessed, can be lightweight, and can be produced in commercialquantities.

Polyacetylene, known as the first conductive polymer, has a disadvantageof its easy oxidation in the air, and it was followed by the developmentof polyaniline, polypyrrole, polythiophene, and the like.

Polyaniline is especially attractive because it is not only relativelyinexpensive and chemically very stable but also easily proton doped.

The polyaniline can be classified into leuco-emeralidine, completelyreduced form, emeraldine, partly oxidized form, and pernigraniline,completely oxidized form, in accordance with its oxidation state.

Because the completely reduced form and completely oxidized form ofpolyaniline have high melting points, they cannot be processed in meltprocessing. Also they cannot be easily processed because they have lowsolubility in solvents with high boiling point such as meta-cresol andin general purpose organic solvents.

To resolve these disadvantages, it had been tried to improve bothprocessability and conductivity by synthesis of graft-copolymers or itsderivatives into which various side chains backbone of the conductivepolymer is induced for enhancing the dissolution. But these compoundshave a much lower electrical conductivity than the conductive polymerbefore reforming.

Many studies described in patents and articles have demonstratedincreased proccessability and conductivity by adding various organicmaterials, polymers or plasticizers.

Among those, a method, which became a turning point for increasingprocessability and conductivity of conductive polymers, used organicsulfonic acid such as camphorsulfonic acid (CSA) orpara-dodecylbenznenesulfonic acid (DBSA) as a dopant of the conductivepolymers.

After that many patents relating to improving conductivity of conductivepolymers are issued. Among those patents, U.S. Pat. No. 6,099,097 andU.S. Pat. No. 6,123,883 proposed methods for processing which add gelinhibitors such as second amines into polyaniline to prevent itsgelation resulted from intermolecular hydrogen bond dissolving highmolecular weight polyaniline, if said polyaniline is in an amount ofmore than 15% by weight to manufactured fibers.

But, the above two U.S. patents have a complex and costly processingprocedure because they require separately adding the second additiveswhich do not make an effect on increasing electrical conductivity of theconductive polymers.

U.S. Pat. No. 5,407,505 describes another processing method ofpolyaniline. This patent proposed liquid composition comprising of astrong acid solution containing polyaniline in which other polymer suchas polypara-(phenylene terephthalamide) were dissolved or a solidcomposition comprising crystalline polyaniline dissolved in acids.However, polyaniline was not easily processed because of dissolving instrong acid, and electrical conductivity was decreased because of theunwanted reactions followed in dissolving procedure, and also thepolyaniline have lower conductivity than pure polyaniline owing toadding polypara-(phenylene terephthalamide).

U.S. Pat. No. 5,882,566 describes a method of manufacturing electricallyconductive fiber with high tension and high modulus usingpolypara-(phenylene terephthalamide). But the polymer in this patent isalso manufactured by dissolving it in sulfuric acid and thus thepolyaniline itself has a sulfonic functional group. As a result thepolyaniline has a disadvantage that its conductivity is reduced asdescribed above. This patent also describes a composition comprisingpolypara-(phenylene terephthalamide) wherein polyaniline has higherelectrical conductivity than polyanilene salt form produced fromsulfonated reactants, but the electrical conductivity of the compositioncomprising polypara-(phenylene terephthalamide) showed 10⁻³˜2.0 S/cm,that is much lower than that of a pure polyaniline salt.

U.S. Pat. No. 5,863,658 reported conductive polymers manufactured frompolymer with rigid rod form of aromatic benzazole and polyanilineincreased electrical conductivity to 128 S/cm. But these polymers seemto be applicable to specific use such as film application becausearomatic benzazole polymer and the polyaniline can be dissolved in onlya strong acid such as methane sulfonic acid. Accordingly, rigid rod formpolymers have very high thermal stability and mechanical properties, butthey are difficult to melt and have a low solubility in solvents.

Besides the patents described above, a lot of research results relatingto conductive polymers were described in detail in a number ofpublications (Organic conductive molecules and Polymers Vol. I–IV, Ed.by H. S. Nalwa, John Wiley & Sons, New York. 1997, Handbook ofConducting Polymers Vol. I, II, Ed. by Skotheim et. al. Marcel Dekker,N.Y. 1998, Conductive Polymers, P. Chandrasekhar, Kluwer Acade. Pub.Boston. 1999).

Thus by reviewing a prior art related to enhancement of the conductivityof the conductive polymers in the patents described above and variousreports, it is concluded that the conductive polymers still do not havehigh enough electrical conductivity and processability forindustrialization.

Conductive polymers have different applications according to electricalconductivity. That is, conductive polymers having the electricalconductivity of 10⁻¹³˜10⁻⁷ S/cm, 10⁻⁶˜10⁻² S/cm, or more than 1 S/cm areapplicable to antistatic materials, static discharge materials, or EMIshielding materials, and semiconductors or solar batteries,respectively. Accordingly upon enhancing the electrical conductivity ofthe polymers, they can be used in more applications.

Consequently, conductive polymers including polyaniline w are limited toextremely limited field, therefore, increasing electrical conductivityand processability of the polymer are needed for various developments ofexpanding their use.

DISCLOSURE OF INVENTION

It is a principal object of the present invention to provide a solubleself-orienting material as an additive for enhancing electricalconductivity of a conductive polymer.

Another object of the present invention is to provide the conductivepolymer having an electrical conductivity of 10³ S/cm that is more 100times than that of a doped pure conductive polymer.

Further object of the present invention is to provide a conductivepolymer composition comprising the additive that can increase thesolubility of the conductive polymer.

In a first aspect, the present invention provides a solubleself-orienting material of monomer form as an additive material forimproving electrical conductivity of a conductive polymer. The solubleself-orienting material of monomer form is shown in General formula 1below:

wherein p is a positive integer indicating size of hydrogen-bond form;A1 is an aromatic ring; X1 and X2 are functional groups which can beindependently selected from —SO₂OH or —COOH as dibasic acid monomer; Z1and Z2 are independently selected from a hydrophilic group, ahydrophobic group or an amphiphilic group).

In a second aspect, the present invention also provides a solubleself-orienting material of metal salt form as an additive material forimproving electrical conductivity of a conductive polymer. The solubleself-orienting material of metal-salt form is shown in general formula 2below:

wherein q is a positive integer; A1 is the aromatic ring; X1 and X2 arefunctional groups independently selected from —CO₂ or —SO₃ as conjugatebase of dibasic acid monomer; Z1 and Z2 are independently selected froma hydrophilic group, a hydrophobic group or an amphiphilic group; M isalkali metal or transition metal of cationic form.

In another aspect, the present invention also provides solubleself-orienting material of a whole aromatic polymer form as an additivematerial for improving electrical conductivity of a conductive polymer.The soluble self-orienting material of a whole aromatic polymer form isshown in General formula 3 below:

wherein r is a positive integer; A1 is the aromatic ring; X1′ and X2′are independently selected from —SO₂, —CO; X3 and X4 are —O—, —NR,wherein R is a side chain independently selected from —H, —CO₂H,—(CH₂)nSO₃H, —(CH₂)nCO₂H or -tert-butyloxycarbonyl; Z1 to Z4 areindependently selected from the hydrophilic group, the hydrophobic groupor the amphiphilic group.

It is desirable that A1 is independently selected from a groupconsisting of phenyl, naphthyl, biphenyl (Φ—Φ; Φ=C₆H₅), benzophenone(Φ-CO-Φ), benzanylide (Φ-CONH-Φ), phenylether (Φ-O-Φ), phenylsulfide(Φ-S-Φ), phenylsulfone (Φ-SO₂-Φ) and phenylsulfoneamide (ΦSO₂NH-Φ). AlsoIt is desirable that Z1 to Z4 include —H and at least one of that is aside chain which is getting 2˜30 length comprising carbon (C), nitrogen(N), sulfur (S) or oxygen (O). Preferably, the side chain is selectedfrom a group consisting of alkyl, akkenyl, alkynyl or laicyclicderivatives independently composed of —(CH₂)nCH₃, —O(CH2)nCH₃, —O(CH₂)nOCH₃, —(OCH₂CH₂)nOCH₃ (n is an integer 1 to 24). Particularly, aterminal end of the side chains contains sulfonic acid(—SO₃H),carboxylic acid (COOH), benzenesulfonic acid (—OC₆H₄SO₃H),benzenecarboxylic acid (—OC₆H₄COOH), azacrwonehter, carbazole, thiol(—SH), pyridinium, imidazol and benzimidazol.

It is desirable that M shown in General formula 2 is Li⁺, Na⁺, K⁺, Cu²⁺,Zn²⁺, Cd²⁺, Mg²⁺, Pb²⁺, Mn²⁺, Fe²⁺, Ca²⁺, Fe³⁺, Ti⁴⁺ or Mn⁷⁺ and that A2shown in General formula 3 is phenyl, naphthal, biphenyl.

It is also desirable that the soluble self-orienting materials arelinear copolymer selected from a group consisting of poly-para-phenyleneterephthalate, poly-para-phenyleneterephthalamide,poly-2,6-naphthaleneterephthalate andpoly-2,6-naphthaleneterephthalamide with a molar ratio of 1˜30% and thematerials have a number average molecular weight of 1,000˜100,000.

In another aspect, the present invention also provides a conductivepolymer composition comprising:

-   an electrically conductive polymer; and-   a soluble self-orienting material of monomer form, as an additive    material for enhancing electrical conductivity of the conductive    polymer, which comprises 1˜95 percent by weight based on the total    composition and shown in General formula 1 below.

wherein p is a positive integer indicating hydrogen-bond form; A1 is anaromatic ring; X1 and X2 are functional groups which can beindependently selected from a group consisting of —SO₂OH, —COOH, —CO2and SO3; Z1 and Z2 are independently selected from the hydrophilicgroup, the hydrophobic group or the amphiphilic group.

In another aspect, the present invention provides a conductive polymercomposition comprising:

-   an electrically conductive polymer; and-   a soluble self-orienting material of metal-salt form, as an additive    material for enhancing electrical conductivity of the conductive    polymer, which comprises 1˜95 percent by weight based on the total    composition and shown in General formula 2 below.

wherein q is an integer of 1 or more; A1 is the aromatic ring; X1 and X2are conjugate base of dibasic acid monomer which can be independentlyselected from —CO₂, —SO₃; Z1 and Z2 are independently selected from thehydrophilic group, the hydrophobic group or the amphiphilic group; M isalkali metal or transition metal of cation form.

In another aspect, the present invention provides a conductive polymercomposition comprising:

-   an electrically conductive polymer; and-   a soluble self-orienting material of whole aromatic polymer form, as    an additive for enhancing electrical conductivity of the conductive    polymer, which comprises 1˜95 percent by weight based on the total    composition and shown in General formula 3 below:

wherein r is an integer of 1 or more; A1 is the aromatic ring; X1′ andX2′ are independently selected from —SO₂, —CO; X3 and X4 are —O—, —NR,wherein R is side chain can be independently selected from —H, —CO₂H,—(CH₂)nSO₃H, —(CH₂)nCO₂H or -tert-butyloxycarbonyl; Z1 to Z4 areindependently selected from the hydrophilic group, the hydrophobic groupor the amphiphilic group.

It is desirable that the conductive polymers are independently selectedfrom polyaniline, polypyrrole, polythiophene, polyacetylene,poly-para-phenylene, polyphenylenesulfide and polycarvazol.

Additional features and advantages of the present invention aredescribed in, and will be apparent from, the detailed description of thepresently preferred embodiments.

DETAILED DESCRIPTION OF THE INVENTION

The additives for a conductive polymer, with above objects, of thepresent invention contain a monomer induced with a flexible side chainhaving various polarities or hydrophilic dibasic acid to aromatic ring,a complex linked by hydrogen bond or metal coordinate bond among themonomer, or a whole aromatic polyamide or a polyester linked repeatedlywith —NRCO—, —NROSO—(R is side chain including hydrogen), and —CO—. Themonomer, complex, polyamide or polyester are linked to aromatic ringabove, respectively.

The additives are based on rigid rod-form polymer self-assembled byhydrogen bond among hydrophilic functional groups or linked not only bymetal coordinate bond but also by —NRCO—, —NROSO— or —OCO—. By inducingflexible long side chain into the aromatic ring of the polymers, itprovides amphiphlicity and possibility of transforming of the conductivepolymer with improved solubility and compatibility, as described in U.S.Pat. No. 5,470,505.

After substituting rigid backbone with normal alkyl group of less than20 of carbon atoms as an flexible side chain, its mechanical, thermaland physical properties were initially investigated by Lenz et al.(Lenz; Eur. J. Polym. 19, p 1043, 1983) and developed by Ballauff(Ballauff et al, Angev. Chem. Int. Ed. Engl. 28, 253, 1989).

The present inventors discovered the following results. On substitutingside chain (i.e. lengthy alkyl alike) to aromatic dibasic acid, thehydrophilic and/or hydrophobic functional groups in monomer hadamphiphlicty and self-orientation to form intermediate phase like liquidcrystal and have orders. Accordingly, inducing these monomers intoconductive polymer, according to the present invention, can change thechain form structure of the polymer.

Based on the fact mentioned above and taking into account of interactionthe conductive polymer, a soluble self-orienting materials (SOM),substituted with various types of side chains with a carbon number 6˜30independently/coordinately to the aromatic ring was synthesized. The SOMwas made up of a monomer/polymer leading self-orientation and was ableto be synthesized through a simple organic polymer reaction.

For example, an aromatic dibasic acid (General formula 1 below) monomerand its metal-salt (General formula 2 below) was produced fromsynthesizing a monomer through simple organic substitution reaction andthen reacting between this acid and metal oxidized material/metalchlorinated material. And polymer (general formula 3 below) could beproduced from a condensation reaction between carboxylic acid and1,4-phenylendiamine or hydroquinone having substitution group.

wherein p, q, or r in General formulas 1, 2, 3, respectively, arepositive integers; X1 and X2 in General formula 1 are independentlyselected from —SO₂OH or —COOH; X1 and X2 in general formula 2 areindependently selected from —CO₂ or —SO₃. X and X2 in general formula 3are independently selected from —O—, —NR—, R is independently selectedfrom —H, —SO₃H, —COOH, —(CH₂)_(n)SO₃H, —(CH₂)_(n)COOH andtert-butyloxycarbonyl; A1 is an aromatic ring and independently selectedfrom phenyl, naphthyl, biphenyl (Φ—Φ; Φ=C6H5), benzophenone (Φ-CO-Φ),benzanilide (Φ-CONH-Φ), phenylether (Φ-O-Φ), phenylsulfide (Φ-S-Φ),phenylsulfone (Φ-SO2-Φ), or phenylsulfoneamide (Φ-SO2NH-Φ); A2 inGeneral formula 3 is a secondary aromatic ring independently selectedfrom pure/sulfonated phenyl, naphthyl or biphenyl;

M in General formula 2 is an alkali or transitional metal cation, whichcan be independently selected from monovalent cation, particularly Li⁺,Na⁺ or K⁺, or a small bivalent cation like Cu²⁺, Zn²⁺, Cd²⁺, Mg²⁺, Pb²⁺,Mn²⁺, Fe²⁺ or Ca²⁺. Also it can be Fe³⁺, Ti⁴⁺, Zr⁴⁺ or Mn⁷⁺; and

Z1 and Z2 in General formula 1, 2, or 3 and Z3 and Z4 in General formula3 above are independently selected from two types of side chain below.

The first side chain is a group inducing stable doping and the secondside chain is a group having affinity with cation or helping movement ofcharges.

More specifically, substituted groups Z1, Z2, Z3, and Z4 areindependently selected and at least one of them contains carbon (C) ornitrogen (N), sulfur (S) and oxygen (O) as a hetero atom. Preferably thegroups contain a side chain of alkyl, alkenyl, alkynyl, or alicyclicderivatives such as norbonene comprising one of —(CH₂)_(n)CH₃,—O(CH₂)_(n)CH₃, —O(CH₂)_(n)CH₃, and —O(CH₂CH₂)_(n)OCH₃ (n is an integer1˜24) with a total length of the side chain of 2˜30, preferably 6˜24.

Also, terminal end of Z1, Z2, Z3 and Z4 may be selected from the sidechains attached to sulfonic acid (—SO3H), carboxylic acid(—COOH), andbenzenesulfonic acid(—OC6H4SO3H) or azacrown ether, carbazole, thiol(—SH), pyridinium, imidazol, and benzimidazol, which have 6˜24 aromaticrings, for stable doping or affinity with cation and charge movement.Especially, self-orienting material attaching pyridinium, imidazol, andbenzimidazol to the terminal end of the side chain is multi-functionalmaterial with a function of a gel-inhibitor, for transferring of stablecation and dopant and also designed for enhancing electricalconductivity and compatibility.

According to the present invention, upon inducing carboxylic group orsulfonic acidic group along with the flexible matrix side chain such assimple alkyl into the rigid aromatic ring, these molecules generally areself-assembled and oriented to form order in a definite concentrationresulted from amphiphilicity.

In the polymer described by General formula 3, it is desirable that thecarboxylic group or the sulfonic acidic group contained in the sidechain is in the range of 1˜15% by weight based on the total polymerweight and have a number average molecular weight of 4,000˜100,000.

Not only can the SOM of the polymer function be a self-orientingmaterial, it also can be a dopant simultaneously by inducing carboxylicgroup or sulfonic acidic group into it, thus it can blend with theconductive polymer without another dopants.

Also, if the cross-section of a hydrophilic molecule and of an alkylgroup in the amphiphilic molecule is almost the same, a layeredstructure is stabilized and the SOM functions as a surfactant. As aresult, the problem of insolubility and unprocessability caused by rigidchain form of the conductive polymer can be solved, as well aselectrical conductivity by inducing chain straightly can be improved, byapplying the SOM to the conductive polymer and extending the concept ofa liquid crystalline phase or a crystalline phase with layer.

For example, if whole aromatic polyamide, which is insoluble andunmeltable, is substituted with two types of flexible matrix side chainsabove to its benzenic ring, it can be soluble in organic solvents suchas 1-methyl-2-pyrrolydinon, 1,1,2,2,-tetrachloroethane, chloroform, andmeta-cresol, form liquid crystalline phase, and meltable as a result ofincreasing thermal fluidity.

Accordingly, a polyamide polymer as the SOM of the present invention,which is a rigid polymer of an aromatic backbone structure linkedrepeatedly with —NRCO— and —NROSO— between 2 benzenic ring substitutedby long side chains, unlike polyparaphenylene terephthalamide (U.S. Pat.No. 5,470,505; U.S. Pat. No. 5,882,566) without side chain, is a polymermaterial having an advantage showing thermal melting behavior because itcan be solved well in ordinary organic solvents.

The polyamide polymer of the present invention, with relatively relievedinteraction such as an intermolecular hydrogen bond by a self-orienteffect of the side chain, has a property to increase an interaction likethe hydrogen bond with the conductive polymer. So, it has increasingcompatibility and prevents gelation by the hydrogen bond betweenpolyaniline molecules. As a result, it has advantage of decreasingpreparation procedure and cost because other additives such as gelinhibitor are not needed for processing.

The SOM above has an ultimate object of maximum electrical conductivityin contained quantity by designing the length of type of the side chainin the aromatic backbone properly and increasing solubility andcompatibility, said backbone can be changed a bit. It is possible thatboth the polymer linked only to para-position with an at least long sidechains and a terpolymer comprising 1˜30% molar ratio of an unbranchedmonomer such as para-phenylenediamine, terephthaloylchloride, or2,6-naphtoylchlride are alike Soluble self-orienting polymers.

These terpolymers refer to a linear polymer which links benzene rings asa monomeric unit at only para position or refers to a linear-curvedcopolymer which links benzene rings at meta or ortho position togetherwith para position. It is well known that melting processibility,solubility and the like of these linear-curved copolymers increasegenerally unlike those of the linear copolymers, which link only paraposition. The present invention also contains a composition comprisingthe linear polymer linked monomeric units at only para position and withthe linear-curved copolymer in order to optimize process procedurealthough the copolymer makes electrical conductivity low.

Electrically conductive polymer according to the present inventionsuitable for enhancing electrical conductivity contains polyaniline,polypyrrole, polythiophene, polyacetylene, poly-para-phenylene,polyphenylenesulfide, polycarbazole alike, especially in doping theconductive polymer of the present invention by a proton such aspolyaniline, polypyrrole, polythiophene even without other dopants. Byinducing the SOM of the present invention, the electrical conductivityof the conductive polymer by inducing chain form of dopant and of theconductive polymer can be increased linearly. Also, because the SOM canenhance solubility, it can apply to any reformed conductive polymer,such as conductive polymer with substitution group or other additives.

Although it is desirable that SOM in molecular weight or in quantityused regularly up to property or use of conductive polymer, it hasself-orienting property as mentioned above and it has no limitedmolecular weight, it can be 1˜99% in quantity.

But, in the SOM of polymeric form, as mentioned above in general formula3, its interaction with the conductive polymer has an important meaningin molecular weight or distribution of molecular weight because terminalend of aromatic backbone is primary amines or carboxylic acid.

For example, in case the number average molecular weight of theconductive polymer is less than 5000, and enhancing processability andphysical property resulted from increasing molecular weight of the SOMby more than 0.2 g/dL of intrinsic viscosity, the effect of terminal enddecreases relatively. But in case the number average molecular weight ofconductive polymer is over 10,000, still more than 30, 000 in range ofallowable mechanical, physical properties, we can lower molecular weightor contained quantity of the SOM above. In this case, the role ofterminal end is relatively large. But, to maximize electricalconductivity, it is desirable that we raise contained quantity of theSOM by more than 50%, preferably by more than 85%, by using varioustypes of SOM respectively.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included to provide a furtherunderstanding of the invention and are incorporated in and constitute apart of this specification, illustrate embodiments of the invention andtogether with the description serve to explain the principles of theinvention.

In the drawings:

FIG. 1 a is a graph showing X-ray diffraction pattern of a existingconductive polymer; and

FIG. 1 b is a graph showing X-ray diffraction pattern of an conductivepolymer composition comprising soluble self-orienting material.

BEST MODE FOR CARRYING OUT THE INVENTION

We will explain in detail the SOM and processing method of itscomposition of the present invention through a desirable example.

To begin, a method to measure electrical conductivity and a method toprocess by synthesizing polyaniline into emeraldine base as a conductivepolymer are described.

<Method to Measure Electrical Conductivity>

Electrical conductivity is measured by a four-line probe method in roomtemperature with a relative humidity 50%. We used carbon paste forcontacting gold wired electrode, and measured electrical current, twoexternal electrodes, and voltage from filmic sample (thickness: t,width: w) with a thickness of 1˜10 μm, and electrical conductivity withregard to distance (1) between two internal electrode with Keithleyconductivity measurement apparatus. Electrical conductivity wascalculated by the formula below, and units of electrical conductivityare in Siemen/cm or S/cm.Electrical Conductivity=(l×i)/(w×t×v)

We measured by Van der Pauw method, which is a standard four pointprobe, for certifying equality of electrical conductivity in samples,but they matched within 5% in result.

<Process for Synthesizing Polyaniline Emeraldine Base>

Polyaniline emeraldine base was synthesized by Mcdiarmid method(Mcdiarmid et al; conducting Polymer Ed. by Alcacer, Dordrecht, 105,1987).

At first, distilled purifying aniline 10 ml and 1M HCl solution 600 mlwas placed into a 3-necked flask, solution of ammonium peroxidesulfate((NH₄)₂S₂O₈) 5.6 g dissolved in 1M HCl 200 ml was added at −5° C. for 15minutes with stirring the solution slowly. 2 hours later, afterfiltering the obtained precipitate with filter paper, it was washed by1M NH₄OH solution 100 ml. After the precipitate was transferred to 0.1 MNH4OH solution 500 ml, stirred for 20 hours and filtered, theprecipitate was dried with vacuum pump for 48 hours and the polyamideemeraldine base 1.5 g was yielded.

EXAMPLES 1a TO 1d

Examples 1a to 1d illustrate the process for synthesizing polyalkylazacrown ether amide (hereinafter referred to as PACA).

i) Example 1a

Example 1a is with regard to a step for synthesizing the primary PACAprecursor. After dissolving diethylterephthalate(DEDHT) 5 g (2.1×10⁻²mol) in dimethylformamide (solvent) 100 ml, K2CO3 base 11.6 g (8.4×10−2mol) was added and stirred in the solution for 30 minutes. Prepared1,10-dibromodecane 28 g (8.4×10−2 mol)/tetrahydrofuran (hereinafterreferred to as THF) solution was added into the solution at 25° C. for 1hour. Then the said mixture was reacted for 48 hours to form a crudeprimary PACA precursor. The precursor was separated and purified withcolumn chromatography to obtain a pure primary PACA precursor 10.8 g(70% yield).

ii) Example 1b

Example 1b is with regard to a step for synthesizing the secondary PACAprecursor. After dissolving the primary PACA precursor 1.0 g (1.4×10−2mol) obtained in example 1a in THT solvent 100 ml, 1,8-diazabicyclo(5.4.0) undec-7-ene (hereinafter referred to DBU) base 0.8 g (5.4×10−2mol) was added. Prepared 1-aza-15-crown-5 0.6 g (2.7×10−3 mol)/THFsolution was added into the solution at 25° C. for 2 hours. Then thesaid mixture was reacted for 48 hours to form a crude secondary PACAprecursor. The precursor was separated and purified with columnchromatography to obtain the pure secondary PACA precursor 1.0 g (75%yield).

iii) Example 1c

Example 1c is with regard to a step for synthesizing the tertiary PACAprecursor.

After dissolving the secondary PACA precursor 1.0 g (9.9×10−4 mol) in0.5 M ethanol solvent 200 ml, the solution was reacted at 25° C. for 12hrs. After titrating hydrolysed solution with 1M HCl to adjust into weakacid, the crude tertiary PACA precursor was formed, separated andpurified with column chromatography to synthesize the pure tertiary PACAprecursor 0.8 g (82% yield).

iv) Example 1d

Example 1d is a step completing PACA polymer.

In ice bath, pyridine 23 ml (3.0×10−1 mol) was added into chlorothionyl(SOCl2) 1.16 ml (6.0×10−3 mol) and the mixture was stirred for 30minutes. After dissolving the tertiary PACA precursor obtained in aboveExample 1c in pyridine 10 ml and adding into the solution, the mixturewas stirred at room temperature for 30 minutes. The reaction solutionwas added into excessive methanol to precipitate and after washing itthree times with water and methanol and drying in vacuum, the PACApolymer 0.75 g (90% yield) was produced.

The above polymer had intrinsic viscosity of 0.2 g/dL. As a result of ananalysis with an infrared spectroscope, it showed a typical amide andC—O absorbance band at 1650 cm−1, 1300 cm−1, and 1120 cm−1.

The reaction mechanism of the above Examples 1a through 1d by steps isshown in Reaction 1 below.

EXAMPLE 2

Example 2 is with regard to a process for synthesizingpolyoligoetoxyazacrownetheramide (hereinafter referred to as POCA),which is one of said SOM of the present invention.

The POCA precursor was synthesized by substituting tosyl group forhydroxy group of triethyleneglycol in the presence of pyridine/THFsolvent. The POCA polymer was synthesized through various steps with thesame process as Example 1. The reaction mechanism is Reaction 2 below.

EXAMPLE 3

Example 3 is with regard to a process for synthesizingpolyalkylcarbazoleamide (PCA).

The PCA precursor was synthesized with the same process as Example 1aand the precursor reacted carbazole in the presence of DBU/THF to inducecarbazole into the terminal end of the side chain. After hydrolyzing theprecursor with the same process as the Examples 1a through 1d, it waspolymerized to form the PCA polymer.

The said polymer had intrinsic viscosity of 0.3 g/dL. Aanalysis with aninfrared spectroscope showed it to have a typical amide and aromaticabsorbance band at 1660 cm−1 and 1600 cm−1. Thermal analysis showed itto have a glass transition point of 160° C. and to stabilize thermallybelow 400° C.

The reaction mechanism in this example 3 is represented by Reaction 3below.

EXAMPLE 4

Example 4 is with regard to a process for synthesizingpolyoligoethoxyamidecarbazole (POAC).

The POAC precursor was synthesized by substituting tosyl group forhydroxy group of triethyleneglycol with the same process as Example 2and the POAC polymer was synthesized through various steps with the sameprocess as Example 3. The reaction mechanism is represented by Reaction4 below.

EXAMPLE 5a

Example 5a is with regard to the SOM material inducing pyridinium intothe terminal end of the side chain of it. With the same procedure asReaction 1, after refluxing the primary precursor and pyridine compoundin the presence of THF solvent for 12 hours and inducing the compoundwith pyridinium the compound was hydrolyzed to obtain a final product.

EXAMPLE 5b

Example 5b is with regard to the SOM material inducing imidazole groupinto the terminal end of the side chain of it. With the same procedureas Reaction 1, imidazole compound (0.1 mol) was dissolved in THF solventand NaOH (0.15 mol) was added into the solution. 30 minutes later, theprimary precursor was added into the solution to make the solutionrefluxed for 6 hrs. The product resulting from the reaction was isolatedwith column chromatography and hydrolyzed to obtain the final product.

The reaction mechanism for Example 5a to 5b is represented by Reaction 5below.

EXAMPLE 6a

Example 6a is with regard to a process for synthesizing carboxylic acidmonomer and polyalkylamide (PAA).

The carboxylic acid monomer is the SOM material of the present inventioncomposed of 12 carbons with carboxylic acid as a substitution group atpara-position. The polyalkylamide is the SOM material of polymeric form.

With the same procedure as the above Example 1a, After dissolvingdiethyl-2,5-dihydroxyterephthalate (DEDHT) 5 g (0.02 mol) in THF solvent100 ml, K2CO3 base 8.168 g (0.06 mol) was added and the mixture wasstirred for 30 minutes.

Solution of 1-bromodecane 10.792 g (0.043 mol) dissolved in THF solventwas added into the solution at 25° C. for 1 hour. After obtainingcarboxylic acid precursor produced from reaction for 24 hours, theprecursor was hydrolyzed with the same procedure as Example 2 tosynthesize carboxylic acid and PAA.

The polymer had intrinsic viscosity of 2.0 g/dL. Analysis with aninfrared spectroscope showed it to have a typical amide and aliphaticabsorbance band at 2,900 and 1650 cm−1. Thermal analysis showed it tohave a glass transition point of 140° C. and to stabilize thermallybelow 260° C. The reaction mechanism is represented by Reaction 6.

EXAMPLE 6b

Example 6b is with regard to the SOM material with a metal complex formof the carboxylic acid monomer produced as shown above in Reaction 6. Abivalent cation such as Ca2+ or Mg2+ can be used for synthesizing themetal complex. After heating Ca (OAC) 2 0.1 mol in NMP solvent todissolve it and hydrolyzed carboxylic acid monomer was added into thesolution, the mixture was reacted at 100° C. for 5 hours to produce themetal complex product. Thermal analysis showed it to stabilize below260° C. and to have a glass transition point of 138°C.

EXAMPLES 7a, 7b

Examples 7a and 7b are with regard to a process for synthesizingbis-dodecyloxybenzene sufonic acid (hereinafter referred to asbissulfonic acid) monomer. The bissulfonic acid monomer is the SOMmaterial of the present invention composed of 12 carbons with thesulfonic acid group as a substitution group at para-position.

The process for synthesizing the bissulfonic acid monomer is representedbriefly in the above Reaction 6, and a more detailed synthesis processis explained in Examples 7a and 7b.

EXAMPLE 7a

Example 7a is with regard to a step for synthesizing bissulfonic acidprecursor.

After dissolving hydroquinone 11 g (0.1 mol) in DMF solvent 100 ml,K2CO3 base 7.6 g (0.3 mol) was added and the mixture was stirred for 30minutes. Prepared 1-bromodecane 75 g (0.3 mol)/DMF solution was addedinto the solution at 55° C. for 1 hour. Crude bissulfonic acid precursorproduced by reacting the solution for 24 hours was isolated and purifiedwith column chromatography to produce the pure bissulfonic acidprecursor 34.7 g (74% yield).

EXAMPLE 7b

Example 7b is with regard to a step for completing the synthesis of abissulfonic acid monomer of the present invention.

After dissolving the bissulfonic acid precursor 22 g (0.05 mol) producedin the above Example 6a in dichloromethane solvent 220 ml,chlorosulfonic acid 11.6 g (0.1 mol) was added into this solution slowlyat 0° C. for an hour. Bissulfonic acid produced by reacting the mixturefor 24 hours was precipitated in hexane solvent, filtrated and washedwith chloroform solvent. The obtained precipitate was dry-vacuumed toform the bissulfonic acid monomer 7 g (20% yield). The reactionmechanism is represented in Reaction 7 below.

EXAMPLES 8a TO 8c

Examples 8a to 8c are with regard to a process for synthesizingpolyphenoxyalkylamide sulfonic acid (PPASA). The synthesis process forPPASA is represented briefly in Reaction 8 below and is explained indetail by steps of Examples 8a through 8c.

i) Example 8a

Example 8a is with regard to a step for synthesizing the primary PPASAprecursor.

After dissolving phenol 10 g (0.1 mol) in THF solvent 100 ml, K2CO3 5.1g (0.2 mol) was added and the mixture was stirred for 30 minutes.Prepared 1,10-dibromodecane 63.8 g (0.2 mol)/THF solution was added intothe mixture at 25° C. for 1 hour. After reaction for 24 hours, producedcrude primary PPASA precursor was isolated and purified with columnchromatography to obtain the pure primary precursor 40 g (68% yield).

ii) Example 8b

Example 8b is with regard to a step for synthesizing the secondary PPASAprecursor.

After dissolving diethyl-2,5-dihydroxyterephthalte (DEDHT) 5 g (0.02mol) in dimethylformamide solvent 100 ml, K2CO3 8.168 g (0.06 mol) wasadded and the mixture was stirred for 30 minutes. The solution 50 ml ofPPASA primary precursor 13.578 g (0.043 mol) obtained in the aboveExample 7a/dimethylformamide was added slowly into the mixture at 25° C.for 10 minutes. After reaction for 24 hours, produced crude secondaryPPASA precursor was isolated and purified with column chromatography toobtain the pure secondary PPASA precursor 10 g (75% yield).

iii) Example 8c

Example 8c is with regard to a step for completing PPASA polymers andcomprising steps for synthesizing the tertiary and quaternary PPASAprecursor as in the prior step.

The PPASA precursor synthesized through the above Example 8b washydrolyzed with the same procedure as in Examples 1c and 1d, and thepolymer was obtained from polymerization. After dissolving the polymerin tetrachloroethane solvent, the PPASA was synthesized throughsulfonation in the presence of chlorosulfonic acid and sulfuric acid.Sulfonation can be regulated to 1–15 percent by weight per gross weightof the PPASA polymer in accordance with reaction period and molar numberadjustment of chlorosulfonic acid and sulfuric acid. The polymer has aintrinsic viscosity of 2.5 g/dL. Analysis with an infrared spectroscopeshowed it to have a typical amide, benzene and S—O absorbance band at1650, 1600, 1520, 1350, and 1100 cm−1. Thermal analysis showed it tohave a glass transition point of 170° C. and stabilize thermally below400° C.

EXAMPLE 9

Example 9 is with regard to manufacturing of a composition comprising ofcarboxylic acid monomer produced in the above Example 6a and polyanilineand with regard to thin-film manufacturing.

After dissolving polyaniline 1 g and carboxylic acid monomer inmeta-crezol/chloroform (weight ratio 1:1) mixed-solvent and filtratingthe solution with 0.2 μm inject filter, the filtrate was placed on theoptical slide glass for spinning. After doping three thin-films, usingspin rates of 1000, 3000 and 5000 rpm respectively, with a thickness ofabout 1 μm in HCl 1M solution, the films were vacuum-dried. Thevacuum-dried samples had electrical conductivity of 72 S/cm, 89 S/cm and94 S/cm respectively. A simply casted sample, for comparison, hadelectrical conductivity of 14 S/cm. It seems that electricalconductivity enhances in proportion to rate owing due toself-orientation of the polymer. In the same conditions, a sample, whichis doped with emeraldine salt without adding SOM with hydrochloride, hadelectrical conductivity of 1.6 S/cm in the range of the above spinningrates, with the reduced value a little bit in proportion to theincreasing rate. Thus, after increasing SOM by only 50% by weight,electrical conductivity increased 50 times, according to the presentinvention.

EXAMPLE 10

Example 10 is with regard to manufacturing of the secondarypolyaniline-SOM composition and with regard to thin-film manufacturing.

After dissolving polyaniline 1.0 g, PAA 0.1 g synthesized in the aboveExample 5 and bis-sulfonic acid 0.15 g synthesized in the above Examples6a and 6b in meta-cresol/chloroform (weight ratio 1:1), mixing thesolvent and filtrating the solution with 0.2 μm filter, the filtrate wasapplied with spinning into optical slide glass at 3,000 rpm.Manufactured film had electrical conductivity of 1,240 S/cm. The filmshowed absorbance at 800–1300 nm with a near-infrared spectroscope,which identified an active transition between polaron and bipolaronbands.

Hereinafter, we explain the property of crystallization degree for thepolyaniline-SOM composition referring to an X-ray diffraction figure.

FIGS. 1 a and 1 b show an X-ray diffraction diagram for a priorconductive polymer and for a conductive polymer composition containingthe soluble self-orienting material of the present invention(hereinafter abbreviated as conductive polymer composition)respectively, wherein the soluble self-orienting material is the PAA andbissulfonic acid monomer of the above Example 9.

FIG. 1 a shows an X-ray diffraction peak for doping the priorpolyaniline emeraldine salt with 1M solution of hydrochloride in theabsence of particular self-orienting materials.

FIG. 1 b shows an X-ray diffraction peak for conductive polymercomposition mixed with polyaniline emeraldine salt and solubleself-orienting material of the present invention with a ratio of 85:15.On comparing FIG. 1 b to FIG. 1 a, FIG. 1 b shows increasing diffractionpeak in the incineration range between 2 and 14 degrees. It is furtherconfirmed that the composition of FIG. 1 b has higher electricalconductivity resulted from adding the above soluble self-orientingmaterial.

Also, the conductive polymer composition of the present inventionexhibits high crystallinity of 40–50% crystallization (crystallizationexcluding orientation effect) seen from the X-ray diffraction diagram inFIG. 1 b.

EXAMPLE 11

Example 11 is with regard to another example for manufacturing of thesecondary polyaniline-SOM composition and with regard to thin-filmmanufacturing.

After dissolving polyaniline 0.8 g and imidazole derivative 0.2 gsynthesized in the above Example 5 in meta-cresol/chloroform (weightratio 4:1), mixing solvent and filtrating solution doped withcamphorsulfonic acid with 0.2 μm inject filter, the filtrate was appliedwith spinning into optical slide glass at 3,000 rpm. The film showedabsorbance at 800–1300 nm with the near-infrared spectroscope, whichidentified an active transition between polaron and bipolaron bands.

Hereinafter, we explain the property of crystallization degree for thepolyaniline-SOM composition referring to an X-ray diffraction figure.

FIGS. 1 a and 1 b show an X-ray diffraction diagram for a priorconductive polymer and for a conductive polymer composition containingthe soluble self-orienting material of the present invention(hereinafter abbreviated as conductive polymer composition)respectively.

FIG. 1 a shows an X-ray diffraction peak for doping the priorpolyaniline emeraldine salt with camphorsulfonic acid in the absence ofparticular self-orienting materials.

FIG. 1 b shows an X-ray diffraction peak for conductive polymercomposition mixed with polyaniline emeraldine salt and solubleself-orienting material of the present invention with a ratio of 80:20.On comparing FIG. 1 b to FIG. 1 a, FIG. 2 b shows increasing diffractionpeak in the incineration range between 2 and 14 degrees. It is furtherconfirmed that the composition of FIG. 1 b has higher electricalconductivity resulted from adding the above soluble self-orientingmaterial.

Also, the conductive polymer composition of the present inventionexhibits high crystallinity of 46–51% crystallization (crystallizationexcluding orientation effect) seen from the X-ray diffraction diagram inFIG. 2 b.

EXAMPLE 12

Example 12 is with regard to manufacturing of PPASA composition producedfrom Example 8a to 8c and to thin-film manufacturing.

The self-dopable film, produced from polyaniline 2 g and PPASA 1 g withthe same procedure as in Examples 8a to 8c, had an electricalconductivity of 2.1×10−2, 5.1×10−3 and 4.4×10−3 S/cm at spinning rate of1000, 3000 and 5000 rpm respectively. Electrical conductivity wasreduced with increasing spin rate and the conductivity was relativelylow due to insufficient doping. On the other hand, the sample processedwith spinning for polyaniline 1 g and PPASA 0.8 g at 1,000 rpm showed anelectrical conductivity of 0.3 S/cm.

Also after doping the same sample with bissulfonic acid using the aboveExample 7a and 7b, electrical conductivity of it increased to 38 S/cm.

EXAMPLE 13

Example 13 is with regard to manufacturing of the tertiarypolyaniline-SOM composition and to thin-film manufacturing.

After heating polyaniline 1 g and PAA 2 g synthesized from the Example6a in 1-methyl-2-pyrrolidinone(weight ratio 1:1) and mixing solvent todissolve it, the solution was filtrated with Whatman #2 filter paper tomake the solution concentrate to 15%. Then the solution was treated witha jetting method, which is scattering water and ethanol with a ratio of3:1 with injection syringe (needle gauge 20), to manufacturemonofilament.

Prepared coagulation bath was adjusted to 40° C. and tip of theinjection syringe was fixed into the solution of the bath. These bluefibers were doped with 1M HCl solution and vacuum-dried for 48 hours.The doping material has an electrical conductivity of 45 S/cm with amethod of 2 point probe. On the other hand, after inducting the SOM inthe form of 0.5M carboxylic acid or sulfonic acid monomer as dopnats,the electrical conductivity was 140 S/cm.

EXAMPLE 14

Example 14 is with regard to manufacturing of the quaternarypolyaniline-SOM composition and to thin-film manufacturing.

Into a 500 ml, 3-necked flask was placed the solution dissolved inethanol 200 ml and was stirred. The solution was neutralized withCa(CO)₃ 0.5 g. After mixing polyaniline 4 g and PAA 4 g into theneutralized solution with the same procedure as Example 9, the mixturewas precipitated and filtered to obtain a filter cake. After drying thefilter cake 8 g and nylon 6 (Toplomid 1011R, Hyosung T&C) 12 g at 80° C.for 24 hours, they were mixed at 240° C., 50 rpm using the Haake Mixer.This mixture was compressed at 235° C. to manufacture the sheet samplewith a thickness of 10 μm. These samples had tensile strength of 70 MPaand electrical conductivity of 0.2 S/cm after doping them with 0.5Mcarboxylic acid and sulfonic acid monomer.

Besides, the electrical conductivity of the sample of polyanilineemeraldine salt with 1M hydrochloride solution in the absence ofparticular additives with that of the sample of the film form of thepolyaniline composition mixing conductive polymers, which with theinduced SOM of a monomer according to the present invention, and withpolyaniline of 15% by weight were 2 S/cm and 1,240 S/cm respectively,that is 620-fold. However, if the contents of polyaniline were less than15% by weight, the polymers had lower electrical conductivity than purepolyaniline emeraldine salt. It means that the SOM is closely connectedwith adjusting of a composition ratio of polyaniline.

Accordingly it is possible for the composition of the present invention,which is mixed with SOM and a conductive polymer, to have the electricalconductivity of 10⁻⁸˜10³ S/cm in accordance with contents of theconductive polymer.

That is, the conductive polymer composition containing the SOM of thepresent invention make SOM occupy 1–95% by weight, desirably 5–85% andmore desirably 15–70%, and maintain the range of the above conductivity.

The conductive polymer composition containing SOM of the presentinvention through above Examples have a function as a dopant andself-orienting promoter. But the present invention is not limited to theabove Examples and may be applied to other forms without departing fromthe essential characteristics thereof.

The conductive polymer composition consisting of the SOM of the presentinvention can be applied to processing of films, fibers, coatings andthe like by precipitating a solution-state composition into otherliquids such as water and by vaporizing solvents of the solution using aprocessing apparatus. Also, the conductive polymer can be processed inthe mater-batch form in a solution state or a melting state respondingwithout or with the second polymer using extruder, injector, orBrabender. Because electrical conductivity of the processed polymer isincreased by spinning rate of screws resulted from properties ofself-orientation and the like of the SOM, those properties can be usedeffectively only if the most suitable conditions are satisfied.

Various metals can be used with used polymers and solvents depending ontemperature and composition of polymers. For example, the SOM containingZn can be used without any difficulties owing to melting over typicalprocessing temperature of 220° C. and the SOM containing Ca is notdissolved over 270° C., but it can be used because it is dissolved in amixed solvent such as hydriquinone and so forth.

Particularly, on coating the composition into steel, Ni, Al, Cu, Zn, Co,Pb, No, Nb, Ag, Ta, Ti, Zr or alloy of steel for anti-corrosion, thatdopants have an anti-corrosive effect resulting from the passivatinganodic sites of acids attached to side chain of the composition.

INDUSTRIAL APPLICABILITY

As mentioned above, the conductive polymer inducing SOM of the presentinvention has higher electrical conductivity, up to 10³ S/cm,significantly higher than that of conventional conductive polymers andhas excellent processibity. So it can be used to all sorts of conductivefilm, fiber, coatings, polymer blending, battery electrode or organicsemiconductor. And the composition has high electrical conductivitynotwithstanding low contents of conductive polymers. So it is suitablefor the particular use such as transparent electrode, anti-corrosion,near-infrared light absorption, conductive etch mask layer and so forth.

The SOM comprises aliphatic compounds, which are self-assembled to thinfilm by langmuir-blogett molecular assembly as mixed agent of conductivepolymer in addition to interfacial active agent. After beingself-assembled, it can be applied to opto-electronic materials accordingto the pattern of the side chains too.

Besides, the SOM has high interfacial adhesion and fusibility and as aresult it can be adapted to various products made by general processingfor thermoplastic resins such as a template for making a model ofnano-particle inorganic materials or fiber, film and coatings requiringconductivity.

1. A soluble self-orienting material of metal-salt form, as an additivefor enhancing electrical conductivity of a conductive polymer,comprising a repeat unit of General formula 2 below:

wherein q is an integer of 2 or more; A1 is an aromatic ring; X1 and X2are conjugate base of dibasic acid monomers which can be independentlyselected from —CO₂; and Each Z1 and Z2 is a side chain selected from agroup consisting of alkyl, alkenyl, alkynyl and alicyclic derivativeswhich is selected from a group consisting of —(CH₂)_(n)CH₃,—O(CH₂)_(n)CH₃ and —O(CH₂CH₂)_(n)OCH₃, wherein n is an integer 1 to 24;M is an alkali metal or a transition metal of cation form.
 2. Thesoluble self-orienting material according to claim 1, wherein M isselected from a group consisting of Li⁺, Na⁺, K⁺, Cu²⁺, Zn²⁺, Cd²⁺,Mg²⁺, Pb²⁺, Mn²⁺, Fe²⁺, Ca²⁺, Fe³⁺, Ti⁴⁺, Zr⁴⁺ or Mn⁷⁺.
 3. Anelectrically conductive polymer composition comprising: an electricallyconductive polymer; and a soluble self-orienting material of metal-saltform, as an additive material for enhancing electrical conductivity ofthe conductive polymer, which occupies 1 to 95 percent by weight basedon the total composition and comprises a repeat unit of General formula2 below:

wherein q is an integer of 2 or more; A1 is an aromatic ring; X1 and X2are conjugate base of dibasic acid monomers which can be independentlyselected from —CO₂; and Each Z1 and Z2 is a side chain selected from agroup consisting of alkyl, alkenyl, alkynyl and alicyclic derivativeswhich is selected from a group consisting of —(CH₂)_(n)CH₃,—O(CH₂)_(n)CH₃ and —O(CH₂CH₂)_(n)OCH₃, wherein n is an integer 1 to 24;M is an alkali metal or a transition metal of cation form.
 4. Thesoluble-self-orienting material according to claim 1, wherein thearomatic ring A1 is selected from a group consisting of phenyl,naphthyl, biphenyl (Φ—Φ; Φ=C6H5), benzophenone (Φ-CO-Φ) benzanilide(Φ-CONH-Φ), phenylether (Φ-O-Φ), phenylsulfide (Φ-S-Φ), phenylsulfone(Φ-SO2-Φ) or phenylsulfoneamide (Φ-SO2NH-Φ).
 5. The solubleself-orienting material according to claim 1, wherein at least one ofthe Z1 to Z2 has the side chain with a length of 2–30, containingcarbon, nitrogen or oxygen.
 6. The soluble self-orienting materialaccording to claim 1, wherein the side chain comprises the alkylderivatives selected from a group consisting of —O(CH₂)_(n)CH₃, or—O(CH₂CH₂)nOCH₃, wherein n is an integer 2 to
 11. 7. The solubleself-orienting material according to claim 1, wherein said side chainhas a substituted terminal end selected from a group consisting ofsulfonic acid (—SO₃H), carboxylic acid (COOH), benzesulfonic acid(—OC₆H₄SO₃H), benzenecarboxylic acid (—OC₆H₄COOH), -azacrownether,-carbazole, thiol (—SH), pyridinium, imidazol and benzimidazol.
 8. Theelectrically conductive polymer composition according to claim 3,wherein the polymer is selected from a group consisting of polyaniline,polypyrrole, polythiophene, polyacetylene, poly-para-phenylene,polyphenylenesulfide or polycarbazole.
 9. The electrically conductivepolymer composition according to claim 3, wherein the solubleself-orienting material is a surface active additive for polymerizationof a corresponding monomer, wherein the monomer is selected from a groupconsisting of aniline, pyrrole, and thiophene.